Water-soluble dyestuffs of the anthraquinone series



United States Patent 3,254,084 WATER-SOLUBLE DYESTUFFS OF THE ANTHRAQUINONE SEREES Richard Fleischhauer, Frankfurt am Main, Fechenheim, and Rolf Miiller, Frankfurt am Main, Germany No Drawing. Filed Oct. 31, 1963, Ser. No. 320,520

Claims priority, applicatizon Germany, Nov. 3, 1962,

6 Claims. (Cl. 260-249) This invention relates to new water-soluble dyestuffs of the anthraquinone series.

More particularly, it relates to water-soluble dyestuffs of the anthraquinone series which derive from the 1,4- diaminoanthraquinone-Z-sulfonic acid and contain, via the amino group in 4-position, the radical of an acylamino-diphenylsul'fone-sulfonic acid linked in m-position (related to the sulfone group), whose acyl radical contains either a substituent which may easily be split off in the form of an anion, or a C 0 double linkage susceptible to addition reactions.

The dyestuffs according to the present invention correspond to the formula r a A SO3H wherein X represents the radical of an acylamino-diphenylsulfone-sulfonic acid linked in m-position whose acylamino radical is contained in that phenyl nucleus of the diphenylsulfone-sulfonic acid which is not directly linked to the anthraquinone radical, said acylamino radical being amember of the group consisting of fi-Chloropropionylamino ,B-Bromopropionylamino fl-Phenylsulfonyl-propionylamino fl-Methylsul-fonyl-propionylarnino ,B-Ethylsulfonyl-propionylamino fl-Phenoxy-propionylamino Acryloylamino fl-Chloracrylolylamino Monochloro-l ,3,5-triazinylamino Dichloro-l,3,5-triazinylamino Monochloro-1,2,4-triazinylamino Dichloro-l ,2,4-triazinylamino Dichloro-diazinylamino Trichloro-diazinylamino Chloropyridazonylamino Chlorodiazinecarbonamide Chlorobenzo-1,3-diazolca1 bonamide Chlorobenzo=1,3-oxazolcarbonarnide ChlorobenZo-1,3-thiazol sulfonamide Such dyestuflfs may be prepared according to known methods, for example by acylating the condensation products obtained from 1-amino-4-bromanthraquinone-Z-sulfonic acid and suitable diaminodiphenylsulfone-sulfonic acids with the corresponding acylating agents. As acylating agents are suited the anhydrides and especially the halides of the carbon acids or chlorazine and chlorazone derivatives hearing at least 2 chlorine atoms.

As acylating agents may be mentioned for example: fl-chloropropionyl chloride, B-bromopropionyl chloride,

3,254,384 Patented May 31, 1966 fi-phenylsulfonyl-propionyl chloride, fi-methylsulfonylpropionyl chloride, ,B-ethylsulfonyl-propionyl chloride, ,B-phenoxy-propionyl chloride, acryloyl chloride, B-chloracryloyl chloride, chlorazineand chlorazol-carboxylic acid chlorides, trichloro-1,3,5- or -l,2,4-triazines, especially cyanuric chloride, dichloro-triazines, trichloro-pyridazines, trichloro-pyrimidines and trichloropyrazines,

. tetrachloro-pyridazine, tetrachloro-pyrimidine, tetrachloro-pyrazine and dichloro-pyridazones.

These acyl radicals may act as so-called reactive radicals because of the substituents contained therein being capable of easily splitting off in the form of an anion, or because of the C C double linkage susceptible to addition reactions, thus imparting to the final dyestuffs the character of reactive dyestuffs.

In the manufacture of the acylated dyestuffs according to the present invention they may be salted out of the resultant aqueous solutions by means of sodium and potassium chloride. They represent, after their separation and drying, deep dark blue powders.

They yield on cotton or regenerated cellulose (spun rayon), when dyed or printed according to a process customary for reactive dyestuffs, deep vivid dyeings or prints which, after rinsing and soaping, possess a very good wet fastness and a very good fastness to light.

Aside from their suitability as reactive dyestuffs, they may be used for the dyeing of animal fibers, such as wool and silk, furthermore polyamide fibers,-leather and paper, whereby also vivid fast dyeings are obtained.

For a better understanding of the nature and objects of' this invention, reference should be made to the accompanying examples which are of an illustrative rather than a limiting nature. Unless otherwise stated, all parts specified are parts by weight and all percentages given are percentages by weight; temperatures given are in degrees centigrade.

Example 1 -72 parts of the initial dyestuffs obtained by condensation of one mol 3,3-diamino-4-methyl-1,1'-diphenyl sulfone-S-sulfonic acid and one mol 1-amino-4-bromanthraquinone-Z-sulfonic acid are dissolved in about 1000 parts of water to give a neutral solution, then 30 parts by volume 4 N sodium acetate solution and '30 parts ,8- phenylsulfonyl-propionic acid chloride are added, and the mixture is stirred for 12 hours at 5-15.", whereby the reaction mixture is kept at a pH of 5-6 by means of 4 N sodium hydroxide solution until a sample is no longer diazotizable. Then the mixture is heated up to 50 and filtered through kieselguhr. The resultant product is salted out by means of sodium chloride separated by suction filtration and dried in the vacuum at about 45.

Yield: parts of a dark blue water-soluble dyestuff powder. dium carbonate, urea and alginate thickening, after drying and subsequently steaming, the dyestuff yields very pure reddish blue prints which after rinsing and soaping are very fast to light and wet processing. When dyed in wool, silk or polyamide fibers, the dyestutf gives also very vivid reddish blue shades of very good fastness properties, whereby the dyebath is completely exhausted.

Preparation of the condensation product used as initial dyestui'f from 3,3-diamino-4-methyl-1,1'-diphenylsulfone- 5-sulfonic acid and 1-amino-4-bromanthraquinone-Z-sulfonic acid:

340 parts 3,3-diamino-4-rnethyl-diphenylsulfone-S-sulfonic acids are dissolved in 3000 parts of water with the When printed on cotton in the presence of soaddition of sodium hydroxide solution to give a neutral solution. Thereupon 3000 parts sodium hydrogen carbonate are added. The solution is heated up to 60, While carbon dioxide is passed through. Subsequently 4-0 parts copper-(D-chloride and in the course of 3 hours 320 parts l-amin-4-bromanthraquinone-2-sulf0nic acid are introduced with stirring, and the mixture is stirred for a further 4 hours at 70. After the addition of 200 parts by volume of a 70% sulfuric acid, the mixture is heated up to 90 and filtered. Subsequently the resultant product is salted out from the hot filtered solution and separated by suction filtration. The filter cake is washed with hot water containing 10% concentrated hydrochloric acid and sodium chloride, and is dried.

Example 2 70 parts of the dyestuff obtained by condensation of one mol 3,3-diamino-4-chloro-1,1-diphenylsulfone-5-sulfonic acid and one mol 1-amino-4-bromanthraquinone-Z-Sultonic acid are dissolved with about 700 parts of Water with the addition of sodium hydroxide solution to give a neutral solution, admixed with 30 parts by volume of a 4 N sodium acetate solution and 12 parts acrylic acid chloride and stirred for 12 hours at 5-15 whereby the solution is kept neutral by means of sodium hydrogen carbonate. When a sample taken from the reaction mixture is no longer diazotizable, the latter is filtered through l ieselguhr and the resultant dyestufi is salted out of the filtrate by means of sodium chloride.

The dried dyestufi yields, when printed on cotton in the presence of sodium carbonate, urea and alginate thickening, after rinsing and soaping, vivid reddish blue prints being fast to light and wet processing.

Example 3 72 parts of a condensation product obtained from 1 mol 1-amino-4-bromanthraquinone-Z-sulfonic acid and 1 mol 3,3'-diamino-4-methyl-1,1-diphenylsulfone-5-sultonic acid are dissolved in about 1000 parts of water with the addition of sodium hydroxide solution to give a neutral solution and stirred at about 25-30 with a solution of 50 parts of the reaction product obtained from cyanuric chloride and 1-B-chloropropionylamino-3-aminobenzene-4-sulfonic acid in the molar ratio 1:1 until such time as a sample taken from the reaction mixture is no longer diazotizable. Then the mixture is heated up to about 60 and filtered. The resultant dyestuif is salted out of the filtrate by means of potassium chloride.

The dried dyestuif yields,'when printed or dyed on cotton according to the methods customary for reactive dyestuffs, very vivid reddish blue shades.

Example 4 72 parts of a condensation product obtained from one mol 1-amino-4-bromanthraquinone-2-sulfonic acid and one mol 3,3-diamino-4-methyl 1,1 diphenylsulfone-S- sulfonic acid are dissolved in about 1000 parts of water with the addition of sodium hydroxide solution to give a neutral solution. into a suspension of 19.5 parts cyanuric chloride in 100 parts ice-water and 60 parts acetone and the liberated mineral acid is neutralized by-the addition of sodium carbonate to such an extent that at the end of the reaction a pH value of 6-7 is obtained. The end of the reaction may be seen from a sample which is no longer diazotizable.

The acylated dyestuff is salted out of the reaction solution obtained. After separating and drying, it represents a dark blue water-soluble powder and, when printed on cotton in the presence of urea, alginate thickening and sodium hydrogen carbonate, it yields vivid reddish blue prints which are fast to light and wet processing.

Containing 2 other reactive chlorine atoms in the acylamino radical, the resultant dyestuff may be condensed in the molar ratio 1:1 with one of the compounds specified in the 'following table, whereby also dyestuffs un- This solution is allowed to run at 0-5 der the invention are obtained which yield, when printed on cotton fabric according to a process customary for reactive dyestufis, the indicated shades:

Shade of the final dyestufi when printed on cotton Ammonia Vivid reddish blue. fi-chlorethylamine Do. Methylamine Do. Ethanolamine D0. Diethanolamine Do.

Isopropylamine Do. Cyclohexylamine Do. Z-amino-benzoic acid Do. 3-amino-benzoic acid Do. 4-arnino-benzoic acid Do. Aminoacetic acid Do. p-amino-ethane-sulfonic acid Do. Methylamino-acetic acid Do. Phenylamino-acetic acid Do. 4-aminobenzene-sulfonic acid Do. 3-aminobenzene-sulfonic acid Do. u-aminopyridine Do. 3-aminophenole Do. 4-aminophenole Do. 3-amino-phenole-6-sulfonic acid Do. 3,5-diamino-benzoic acid Do. 2,4-diamino-benzoic acid Do. 2,4-diamino-t-oluene Do. 2,4-diaminobenzene-sulfonic acid Do. 2,5-diaminobenzene-sulfonic acid Do. 2-amino-5-naphthol-7-sulfonic acid Do. 1-amino-8-naphthol-3,6-disulfonic acid Do. P'henole-4-sulfonic acid Do. Phenole Do. Methylmercaptane Do. 1-amino-8-naphthol Do. 1-amino-5-naphthol Do. Thiophenole Do. l-aminobenzene-3-sulfonamide Do. 1-aminobenzene-3-(,B-chlorethyl) sulfonamide Do. Potassium rhodanide Do. 4-aminopl1enole-2-carboxylic acid D0. 4-aminophenole-G-sulfonic acid-2- carboxylic acid a Do.

Using as acylating' agent in the above example instead of the cyanuric chloride equivalent amounts of 2,4,5,6-tetrachloropyrimidine 2,5 ,6-trichlorotriazine-( 1,3 ,4)

3,4,5,6-tetrachloropyridazine 2,3,5,6-tetrachloropyrazine 2,3-dichloropyrazine-5-carboxylic acid chloride or 2,3-dichloro-5,6-benzo-pyrazine-5'-carboxylic acid chloride,

dyestuffs of similar valuable vivid shades and fastness properties are obtained.

Example 5 34.2 parts 3',4-diamino-6'-methyl-1,1'-diphenylsulfone- 2-sulfonic acid are dissolved in water with the addition of the necessary amount of sodium hydroxide solution to give a neutral solution. Subsequently 50 parts sodium hydrogen carbonate are added and the solution is heated up to a temperature ranging between and while carbon dioxide is introduced. The mixture is admixed with one part copper-(I)-chloride and one part copper powder and at 70 with 38.2 parts 1-amino-4-bromanthraquinone-Z-sulfonic acid, subsequently it is stirred for some hours at a-temperature of 70 to The reaction mixture is, if necessary, subsequently diluted with water and the copper containing precipitate is separated by suction filtration. After the filtrate has been acidified with hydrochloric acid, the resultant dyestutf is precipitated by means of sodium chloride, filtered 01f and washed out by means of hot salt solution containing hydrochloric acid. The residue obtained is a dark water-soluble dyestutf paste.

Such an amount of this dyestulf paste as corresponds to 64.3 parts of the dry dyestufi powder, is dissolved in water with the addition of sodium hydroxide solution to give a neutral solution. At 0 to 3", this solution is allowed to run into a suspension of 19 parts cyanuric chloride, 190 parts of acetone and 300 parts of ice-water. While the liberated mineral acid is neutralized by the addition of a sodium carbonate solution, the mixture is stirred until such time as a sample taken therefrom is no longer or only weakly diazotizable and at the end of the reaction a pH value of 6-7 is obtained. The reaction product is separated out of the resultant dyestuif solution by salting out with potassium chloride or mineral salt and filtered off. The residue is then washed with some acetone and dried in the vacuum. A dark blue water-soluble dyestuff powder is thus obtained which yields, when printed on cotton in the presence of sodium carbonate or sodium hydrogen carbonate, urea and alignate thickening accord-' fonic acid and by reacting the resultant condensation product with cyanuric chloride or with equivalent amounts of 2-(4-sulfonylamino)-4,6-dichloro-triazine- 1,3,5)

Example 6 Such an amount of the dyestulf paste obtained according to Example 5, paragraph 1, hereinbefore as correspond to 64.3 parts of the dry dyestuff powder is dissolved in water with the addition of excess sodium hydrogen carbonate. At 5-10, 26 parts B-phenylsulfonyl-propionylchloride are allowed to run into this solution and the mixture is stirred until such time as a sample taken therefrom is no longer diazotizable. After separating and drying, the reaction product represents a water-soluble dark blue dyestufl which yields, when printed on cotton or viscose rayon in the presence of sodium carbonate, urea and alginate thickening, very vivid reddish blue prints which are fast to light and wet processing.

Replacing in the above example the ,B-phenylsulfonylpropionic acid chloride proposed as acylating agent by fl-chloropropionic acid chloride, B-bromopropionic acid chloride or fi-ethylsulfonyl-propionic acid chloride, dyestufls of similar good tinctorial properties are obtained.

The following table enumerates further dyestuffs under the present invention which are obtained by acylation of the 4 (amino phenylsulfone phenylamino) 1 aminoanthraquinone-2-sulfonic acids mentioned with the indicated acylating agents and which possess the shades indicated in the last column:

Anthraquinone derivative Acylating agent Shade of the final dyestufi 0 NH; II I g s 03H C1-C.CH=CH2 Reddish blue.

II O N SO NH2 Same as shov C1.CO.CH2.CH2.C1 Vitvlid reddish Same as above C1.CO.CH=CH.C1 Do.

Same as abov 01.0 001120112. o-Q Do.

Same as abovp CI.OO.CH2.CHZ.SOZ.OH Do.

Same as above 01 W |NH Do.

I V o 0 OH Same as abov G1 I FNH- Do.

I V o 0 OH I Cl Same as abov Cl l lNH 303E Do,

V I C1 N Same as above (ll-f Cl Do.

Anthmquinone derivative Acylating agent Shade of the final dyestufl O NHz N C1 O1 Vivid reddish so H blue.

A N S0 NH2 Same as abov Do.

C1- N}C1 (I) 0.01' Same as abov T Do.

C1 N)O1 Same as abov O1 Do.

Same as above"... C1 D0.

N Same as abovP O1 Do.

N Same as a ov Ol O1 Do.

C1 N C1 N Same as abov C1- Do.

, N I Same as above.. Ol

: L DO.

Same as abovem N Do.

i[ O1.02S S Same as above. 01.0 0 N I D Same as above Anthraquinone derivative Acylating agent Shade of the final dyestufi O NH; Cl Vivid reddish )K blue.

CJ1-I I I C1 N G1 l COOH $0311 SOQH O NHz II I [I I 50311 II I O NH SO2- NH2 O NHz II I (Us 0&1

II I O NH- SOP NHi CH3 CH3 O NH:

II I A -SO H II 0 NH -SO NH:

CH3 SOaH O NH: I

( NH SO NH:

CH3 S0311 Same as above -Q Same as above Same as above...

Anthraquinbne derivative Acylating agent; Shade of the final dyestufi 0 NH; 01 Vivid reddish I blue. I l S 0 311' TI I C l )-Cl (i l IH S O NH2 l C O O H 0 11 O NH; II I H l 50 E XQ-smn D0.

J N N I O NH S O NH: C1-KN J-Cl l S 03H What we claim is:

1. Water-soluble anthraqui'none dyestufis of the formula l wherein X is a radical of an acylamino-1,1-diphenylsulfone-sulfonic acid linked in m-position (related to the sulfone radical) whose acylamino radical is contained in that phenyl nucleus which is not directly linked to the anthraquinone radical, said acylamino radical being a member of the group consisting of Chlorobenzo-1,3-diazol carbonamide Chlorobenzo-1,3-oxazol carbonamide Chlorobenz-o-1,3-thiazol sulfonamide.

2. 3 [1" amino 2" sulfo anthraquinonyl (4"-)- amino] 3 acylamino 1,1 diphenylsulfone 5' sulfonic acid, wherein acylamino has the meaninggiven in claim 1.

.3. 3 [1" amino 2" sulfo anthraquinonyl (4"-)- amino] 3' acylamino 4 methyl 1,1 diphenylsulfone-5-'sulfonic acid, wherein acylamino has the meaning given in claim 1.

4. 3 [1" amino 2" sulfo anthraquinonyl (4"-)- amino] 3 acylamino 6' methyl 1,1 diphenylsul fone-4-sulfonic acid, wherein acrylamino has the meaning given in claim 1.

5. 3 [1" amino 2" sulfo anthraquinonyl (4"-)- amino] 2 acylamino 1,1 --diphenylsulfone '4' sulfonic acid, wherein acylamino has the meaning given in claim 1.

6. 3 [1" amino 2" sulfo anthraquinonyl (4"-)- amino] 4' acylamino 6 methyl 1,1 diphenylsulfone-2'-su1fonic acid, wherein acylamino has the meaning given in claim 1.

References Cited by the Examiner UNITED STATES PATENTS 3,078,281 2/1963 Braun et a1. 260372 JOHN D. RANDOLPH, Acting Primal Examiner. WALTER A.'MODANCE, Examiner. I. M. FORD, Assistant Examiner. 

1. WATER-SOLUBLE ANTHRAQUINONE DYESTUFFS OF THE FORMULA 